Laminate, laminate for adhering, adhesion method, method for manufacturing laminate, electrolyte film, and electronic device

Abstract

[Problem] To provide a laminate and similar that have a wide application range. [Solution] One embodiment of the present invention provides a laminate. In this laminate, an electrode, an electrolyte membrane, and an ion transfer layer for transferring ions to and from the electrode are laminated in this order. The electrolyte membrane includes an elastomer and an ionic compound. The average film thickness of the electrolyte membrane is 15 μm or less.

Description

Laminate, laminate for application, application method, method for manufacturing laminate, electrolyte membrane, and electronic device

[0001] The present invention relates to a laminate, a laminate for application, an application method, a method for producing a laminate, an electrolyte membrane, and an electronic device.

[0002] In recent years, there has been active development of wearable devices that can be attached to the skin. For example, Patent Document 1 discloses a textile-type device that is less uncomfortable to wear and solves problems with deformation and conformability.

[0003] International Publication No. 2017 / 065272

[0004] The device disclosed in Patent Document 1 is wired with conductive threads or wires. Meanwhile, in recent years, there has been a demand for the development of wearable devices for various applications, such as displays.

[0005] In view of the above circumstances, the present invention provides a laminate and the like that has a wide range of applications.

[0006] According to one aspect of the present invention, there is provided a laminate. The laminate includes an electrode, an electrolyte membrane, and an ion exchange layer that exchanges ions with the electrode, stacked in this order. The electrolyte membrane includes an elastomer and an ionic compound. The average thickness of the electrolyte membrane is 15 μm or less.

[0007] According to the above aspect, a laminate or the like having a wide range of applications is provided.

[0008] FIG. 1 is a cross-sectional view of an example of a laminate according to the first embodiment. FIG. 2 is a cross-sectional view of an example of a laminate according to the first embodiment. FIG. 3 is a conceptual diagram for explaining the effect of a laminate to which the electrolyte membrane 11 of the first embodiment is applied. FIG. 4 is a cross-sectional view of an example of a laminate for application according to the second embodiment. FIG. 5 is a conceptual diagram showing an example of an application method according to the second embodiment. FIG. 6 is a graph summarizing the results of evaluation of the devices obtained in the examples. FIG. 7 is a photograph showing the results of evaluation of the devices obtained in the examples.

[0009] Hereinafter, embodiments of the present invention will be described. Note that the various features shown in the following embodiments can be combined with each other. In addition, in this specification, "~" means "above" through "below" unless otherwise specified.

[0010] <First embodiment: laminate> The laminate of this embodiment is as follows: A laminate comprising an electrode, an electrolyte membrane, and an ion exchange layer that exchanges ions with the electrode, stacked in this order, the electrolyte membrane containing an elastomer and an ionic compound, and the electrolyte membrane having an average thickness of 15 μm or less. The layers that constitute the laminate of this embodiment, its uses, and the like will be described below with reference to the drawings.

[0011] Fig. 1 is a cross-sectional view of an example of a laminate according to the first embodiment. The laminate 100 shown in Fig. 1 is formed by stacking an electrode 12, an electrolyte membrane 11, and an ion exchange layer 13. The ion exchange layer 13 is a layer that exchanges ions with the electrode 12. In addition, the laminate 100 shown in Fig. 1 has a first insulating layer 14 and a second insulating layer 15 provided as outermost layers.

[0012] Such a laminate (a laminate including at least the electrode 12, the electrolyte membrane 11, and the ion exchange layer 13) may be applied to various applications. Typically, the laminate of this embodiment may constitute a part of various electronic devices. Examples of electronic devices include displays, transistors, secondary batteries, solar cells, and various sensors. In this embodiment, the laminate may constitute a part of a display or a transistor. That is, in the laminate of this embodiment, ions can be exchanged between the electrode 12 and the ion exchange layer 13 via the electrolyte membrane 11. By utilizing this function, various electric elements can be manufactured.

[0013] In the laminate 100 of this embodiment, since the average thickness of the electrolyte membrane 11 is low, the average thickness of the entire laminate 100 can easily be set to a low level. That is, the average thickness of the laminate 100 of this embodiment may be 50 μm or less, 40 μm or less, or 30 μm or less. The lower limit of the average thickness of the laminate 100 is not particularly limited, but an example is 1 μm or more.

[0014] Each layer that can form the laminate 100 will be described below.

[0015] (Electrolyte Membrane 11) The electrolyte membrane 11 of this embodiment is a layer (membrane) interposed between the electrode 12 and the ion exchange layer 13. The electrolyte membrane 11 of this embodiment is characterized by including an elastomer and an ionic compound. The materials constituting this electrolyte membrane 11 will be described below.

[0016] Elastomer: In this embodiment, an elastomer refers to a polymeric substance having elasticity. This elastomer is typically a material that stretches when subjected to tension and returns to approximately its original length when the tension is released. Examples of this elastomer include hydrocarbon elastomers such as natural rubber, isoprene rubber, nitrile rubber (NBR), ethylene propylene rubber (EPDM), styrene-butadiene rubber (SBR), butadiene rubber (BR), and chloroprene rubber (CR), as well as hydrogenated elastomers thereof; silicone elastomers; fluoroelastomers; urethane elastomers; acrylic elastomers; polyester elastomers; polyamide elastomers; polyimide elastomers; polyrotaxanes; and the like. These may be used alone or in combination. Alternatively, a composite elastomer in which two or more elastomers are chemically bonded may be used as the elastomer of this embodiment.

[0017] The elastomer of this embodiment preferably contains a heteroatom in its chemical structure. As will be described later, the electrolyte membrane 11 of this embodiment contains an ionic compound. From this perspective, when the elastomer contains a heteroatom in its chemical structure, the affinity with the ionic compound is likely to be improved. As a result, a highly uniform electrolyte membrane 11 is likely to be obtained.

[0018] Here, the heteroatom is, for example, selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom. To give a more typical example, the elastomer of this embodiment preferably has a chemical bond containing a heteroatom in its chemical structure. That is, the elastomer of this embodiment preferably has, in its chemical structure, one or more bonds selected from the group consisting of an ether bond, a sulfide bond, an ester bond, a thioester bond, an amide bond, and a urethane bond. Among these, from the viewpoints of high availability and ease of imparting durability to the obtained laminate 100, it is preferable that the elastomer of this embodiment contains a urethane bond in its chemical structure.

[0019] Ionic Compound The ionic compound of this embodiment is a compound having a cation moiety and an anion moiety (in other words, a salt compound).

[0020] The cation moiety constituting the ionic compound can be appropriately selected, and examples thereof include alkali metal cations; quaternary ammonium cations; imidazolium cations; pyridinium cations; piperidinium cations; pyrrolidinium cations; quaternary phosphonium cations; trialkylsulfonium cations; pyrrole cations; pyrazolium cations; and guanidium cations. Among these, it is more preferable to employ alkali metal cations; quaternary ammonium cations; imidazolium cations; pyridinium cations; piperidinium cations; pyrrolidinium cations; quaternary phosphonium cations, or trialkylsulfonium cations as the cation moiety. In this specification, the term "type" is used to refer to a specific chemical structure, but also to a structure substituted with any substituent. For example, "imidazolium cations" is used to refer to a (unsubstituted) imidazolium cation, as well as a structure having substituents such as alkyl groups at positions 1 to 5 of the imidazole ring.

[0021] The anion moiety constituting the ionic compound can be appropriately selected, but SCN － , B.F. ４ － , P.F. ６ － , NO ３ － , C.H. ３ COO － , C.F. ３ COO － , C.H. ３ SO ３ － , C.F. ３ SO ３ － , (FSO ２ ) ２ N － , (CF ３ SO ２ ) ２ N － , (CF ３ CF ２ SO ２ ) ２ N － , (CF ３SO ２ ) ３ C － , AsF ６ － , SbF ６ － , NbF ６ － , TaF ６ － , (CN) ２ N － , C ４ F ９ SO ３ － , (C ２ F ５ SO ２ ) ２ N － , C ３ F ７ COO － , B(CN) ４ － , C(CN) ３ － , N (CN) ２ － , C.H. ３ OSO ３ － , C ２ H ５ OSO ３ － , C ４ H ９ OSO ３ － , C ６ H １３ OSO ３ － , C ８ H １７ OSO ３ － , p-toluenesulfonate anion, (C ２ F ５ ) ３ PF ３ － , chloride ion, bromide ion, iodide ion, etc.

[0022] The ionic compound of this embodiment is preferably a non-volatile molten salt (which may also be referred to as an "ionic liquid") that is liquid (liquid state) anywhere within the range of 0 to 150° C. The ionic compound of this embodiment can be used alone or in combination of two or more kinds.

[0023] The amount of the ionic compound contained in the electrolyte membrane 11 of this embodiment can be set appropriately depending on the application, etc. When the mass of the elastomer contained in the electrolyte membrane 11 is taken as 100 parts by mass, the mass of the ionic compound contained in the electrolyte membrane 11 is preferably in the range of 1 part by mass to 50 parts by mass, more preferably 3 parts by mass to 45 parts by mass, and even more preferably 5 parts by mass to 40 parts by mass. Setting the amount in such a range makes it easier to balance the conductive properties and mechanical properties of the electrolyte membrane 11.

[0024] In addition, the electrolyte membrane 11 may contain various other components within the scope of the present invention. Typically, the electrolyte membrane 11 may further contain other components such as an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a thermal stabilizer, a lubricant, an antistatic agent, a brightener, a colorant, a release agent, a surface treatment agent, a flame retardant, various fillers, and a crosslinking agent. Examples of crosslinking agents include polyfunctional vinyl compounds such as divinylbenzene, triallyl cyanurate, triallyl isocyanurate, and diallyl phthalate; and polyfunctional (meth)acrylate compounds such as ethylene glycol di(meth)acrylate, diethylene glycol, and polyethylene glycol di(meth)acrylate. In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. When the electrolyte membrane 11 contains the above-mentioned other components, the amount of each component is appropriately determined depending on the purpose.

[0025] Furthermore, the present embodiment is characterized in that the average thickness of the electrolyte membrane 11 is 15 μm or less. That is, in the laminate 100 of the present embodiment, the low average thickness of the electrolyte membrane 11 facilitates expanding the range of uses of the laminate 100. The average thickness of the electrolyte membrane 11 may be 12 μm or less, 10 μm or less, 7 μm or less, 5 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less. The lower limit of the average thickness of the electrolyte membrane 11 is not particularly limited, but an example is 0.01 μm or more. This average thickness can be calculated, for example, as the average value of any five points measured by cross-sectional observation using a scanning electron microscope. An electrolyte membrane 11 having such a thin thickness can be produced, for example, by a method described below.

[0026] (Electrode 12 / Ion-exchange layer 13) In this embodiment, the electrode 12 exchanges ions with the ion-exchange layer 13. That is, depending on the properties of the ion-exchange layer 13, the electrode 12 may be an anode or a cathode.

[0027] The electrode 12 and the ion exchange layer 13 in this embodiment are made of a conductive material. Specific examples of the conductive material include, but are not limited to, metals (silver, gold, copper, etc.), carbon (graphite, carbon black (acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.), carbon nanotubes (single-walled, multi-walled, and mixtures thereof), conductive polymers, and mixtures thereof.

[0028] The electrode 12 and the ion exchange layer 13 may contain various electrochromic materials. Electrochromic materials are materials whose light transmittance can be reversibly changed by applying a voltage. More specifically, these materials reversibly change the absorption spectrum of visible light by applying a voltage, thereby coloring or decoloring the material.

[0029] The electrochromic substance may be either an inorganic electrochromic compound or an organic electrochromic compound. That is, the electrochromic substance may be a dye-based, polymer-based, metal complex-based, or metal oxide-based electrochromic compound, or a carbon-based material. In the first embodiment, the electrochromic substance is preferably a conductive polymer that exhibits electrochromism.

[0030] As a more typical example, the electrode 12 and / or the ion-accepting layer 13 may include one or more polymers selected from the group consisting of polythiophene, polypyrrole, polyaniline, and polybenzodifurandione, which can function as the electrochromic material described above.

[0031] To give a more specific example, the electrode 12 and / or the ion-accepting layer 13 may contain a polythiophene having a structural unit represented by the following chemical formula (1).

[0032] In chemical formula (1), each R is independently an organic group, a hydroxyl group, a mercapto group, an amino group, or a halogen atom, and the structure of R may have an anionic structure as part of its structure, and n is an integer of 0 to 4.

[0033] That is, a polythiophene having a structural unit represented by chemical formula (1) can function as an electrochromic material. More specifically, if the ion-accepting layer 13 contains a polythiophene having a structural unit represented by the aforementioned chemical formula (1), when a voltage is applied to the electrode 12, the electronic state of the polymer contained in the ion-accepting layer 13 changes. As a result, the color of the polymer changes (becomes colored), and a predetermined image can be generated. Of course, both the electrode 12 and the ion-accepting layer 13 may contain the above-mentioned polymer.

[0034] In chemical formula (1), any organic group can be used as R. In one aspect, R may be a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkaryl group, cycloalkyl group, alkoxy group, heterocyclic group, carboxy group, or the like. With regard to the organic group that can be contained in R, examples of the number of carbon atoms contained in the organic group include 1 to 30.

[0035] In a more typical example, the organic group that can be used as R may be a group represented by the following chemical formula (2).

[0036] In the chemical formula (2), * represents a bond, and Y １ represents a single bond, —O—, —S—, —C(O)—, —C(O)O—, and —C(O)NR １ - is selected from the group consisting of Y ２ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, some of the carbon atoms constituting the alkylene group may be substituted with oxygen atoms; Y ３ represents a single bond, —O—, —S—, —C(O)—, —C(O)O—, and —C(O)NR １ - is selected from the group consisting of Y ４ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, some of the carbon atoms constituting the alkylene group may be substituted with oxygen atoms, and R １ represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, Z represents a linear or branched alkyl group having 1 to 5 carbon atoms, —COOH, —COO － , -SO ３ H and -SO ３ － is selected from the group consisting of:

[0037] Among these, Y １ is preferably a single bond. ２is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and even more preferably a linear or branched alkylene group having 1 to 4 carbon atoms. ２ When Y is an alkylene group, some of the carbon atoms constituting the alkylene group may be substituted with oxygen atoms. ３ is preferably —O—. ４ is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and even more preferably a linear or branched alkylene group having 1 to 4 carbon atoms. ４ When Z is an alkylene group, some of the carbon atoms constituting the alkylene group may be substituted with oxygen atoms. ３ H or -SO ３ － It is preferable that:

[0038] In the above chemical formula (1), n ​​is preferably 0 to 2, and more preferably 0 or 1. When the R moiety contains an anionic structure, the thiophene ring typically becomes cationic, but for convenience, this aspect is omitted from the above chemical formula.

[0039] Furthermore, when a polythiophene having a structural unit represented by the above-described chemical formula (1) is used as the polymer that can be contained in the electrode 12 and the ion exchange layer 13, the polythiophene may contain structural units other than the structural unit represented by the above-described chemical formula (1). For example, the polythiophene may contain structural units derived from (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylic acid amides, styrene, hydroxystyrene, styrenesulfonic acid, etc., and the amount of such structural units is also optional. For example, when a structural unit derived from styrenesulfonic acid is contained, the moiety derived from this sulfonic acid moiety can function as a dopant.

[0040] Furthermore, the electrode 12 and the ion exchange layer 13 may contain a polymer selected from the group consisting of polypyrrole, polyaniline, and polybenzodifurandione. Here, polybenzodifurandione is an organic polymer having a benzodifurandione skeleton. Polybenzodifurandione is typically a compound having a structural unit represented by the following chemical formula (3). Note that, although there are chemical structures that are conjugated with the following chemical formula (3), the details are omitted in this specification. That is, the polybenzodifurandione in this embodiment may be a polymer having a chemical structure that is conjugated with the following chemical formula (3).

[0041]

[0042] In addition, in the chemical formula (3), R ３１ ~R ３４ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a phenyl group which may have a substituent, and a naphthyl group which may have a substituent. The substituent on the phenyl group or naphthyl group is a group which replaces some of the hydrogen atoms present in the phenyl group or naphthyl group, and examples thereof include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and a phenyl group. The number of substituents on the phenyl group or naphthyl group can be set as appropriate, and is set, for example, in the range of 1 to 4 or 1 to 3.

[0043] Representative examples of the polybenzodifurandione include benzodifurandione paraphenylene vinylidene (BDPPV) and PBDF as described in J. Am. Chem. Soc. 2023, 145, 3706-3715. That is, the polybenzodifurandione in this embodiment may be a polymer containing, in addition to the structural unit represented by the above-mentioned chemical formula (3), a structural unit different from the structural unit represented by the above-mentioned chemical formula (3).

[0044] Additionally, the electrode 12 and the ion-accepting layer 13 may contain components other than polythiophene (typically a polymer containing the structural unit represented by the above-mentioned chemical formula (1)) and polypyrrole, polyaniline, and polybenzodifurandione, as long as they do not deviate from the spirit of the present invention. For example, the electrode 12 and the ion-accepting layer 13 may contain various components, such as the elastomer, ionic compound, and other components described with respect to the electrolyte membrane 11, as well as a conductivity imparting agent such as polyvinyl alcohol. Alternatively, the electrode 12 and the ion-accepting layer 13 may be composed solely of one or more polymers selected from the group consisting of polythiophene, polypyrrole, polyaniline, and polybenzodifurandione. This facilitates the realization of an electrode 12 and an ion-accepting layer 13 that are easy to manufacture industrially. Note that when the above-mentioned various polymers are used as the electrode 12 and the ion-accepting layer 13, typically, one polymer (e.g., the polymer used in the electrode 12) is a p-type compound, and the other polymer (e.g., the polymer used in the ion-accepting layer 13) is an n-type compound. In many instances, the polymers applied to the electrode 12 and the ion-accepting layer 13 are different polymers.

[0045] In the laminate of this embodiment, at least one of the electrode 12 and the ion exchange layer 13 may be a patterned film. That is, while FIG. 1 shows the laminate 100 in which each layer has the same structure, the laminate of this embodiment may be the one shown in FIG. 2. FIG. 2 is a cross-sectional view of an example of the laminate according to the first embodiment. In the laminate 200 shown in FIG. 2, the electrode 22 and the ion exchange layer 23 are shown as being patterned. In addition, the electrolyte membrane 21, the first insulating layer 24, and the second insulating layer 25 may be the same as the electrolyte membrane 11, the first insulating layer 14, and the second insulating layer 15 shown in FIG. 1, respectively.

[0046] As described above, when at least one of the electrode 12 and the ion exchange layer 13 is a patterned film, this can contribute to improving the performance of the electronic device (higher resolution as a display), as will be described in detail below.

[0047] 3A and 3B are conceptual diagrams illustrating the effect of a laminate employing the electrolyte membrane 11 of the first embodiment. As shown in FIG. 3A, a system is assumed in which two electrodes (electrodes 12A and 12B) arranged in a line pattern and an ion exchange layer 13 are arranged with the electrolyte membrane 11 interposed therebetween. It is also assumed that a predetermined voltage is applied only to the electrode 12A. In this case, if a thin electrolyte membrane 11 such as that shown in the first embodiment is employed, the movement of ions to the ion exchange layer 13 takes precedence over the movement of ions from the electrode 12A to the electrode 12B, and therefore only the electrode 12A operates. (When an electrochromic material such as that described above is used, only the electrode 12A is colored (see FIG. 3B).) On the other hand, if an electrolyte membrane thicker than the electrolyte membrane 11 shown in the first embodiment is used, the degree of ion movement from the electrode 12A to the electrode 12B and the degree of ion movement to the ion exchange layer 13 become equal, and both the electrode 12A and the electrode 12B can operate (if an electrochromic material as described above is used, both the electrode 12A and the electrode 12B become colored (see FIG. 3(c))). In this way, by using a thin film as shown in the first embodiment as the electrolyte membrane 11 and making at least one of the electrode 12 and the ion exchange layer 13 a patterned film as described above, a device with high resolution can be easily realized.

[0048] (First insulating layer 14 / second insulating layer 15) The laminate 100 of this embodiment may further include a first insulating layer 14 and a second insulating layer 15 as outer layers of the electrode 12 and the ion exchange layer 13, respectively. These various insulating layers may be appropriately selected from materials that can insulate the electrode 12 and the ion exchange layer 13 from the outside. As an example, they may be made of the various elastomers described above, but the present invention is not limited thereto, and these layers may be made of various insulating materials.

[0049] (Method for manufacturing the laminate 100) Next, a method for manufacturing the laminate 100 will be described. The method for manufacturing this laminate includes a step of stacking the electrode 12, the electrolyte membrane 11, and the ion exchange layer 13. That is, the method for manufacturing the laminate 100 of this embodiment involves stacking each layer. Here, this stacking may be achieved by stacking layers that have been fabricated in advance, or by providing a new layer on another layer that has already been fabricated.

[0050] In the laminate 100 of the present embodiment, the average film thickness of the electrolyte membrane 11 is controlled to a low level. Typically, the electrolyte membrane 11 may be obtained by applying a chemical solution containing an elastomer, an ionic compound, and a solvent to a substrate, and then drying the applied solution to form a film.

[0051] That is, the method for producing the laminate in this embodiment may be performed by preparing a chemical solution containing an elastomer and an ionic compound in a predetermined ratio and then forming a thin film from the chemical solution. Various methods can be used to apply the coating to the substrate. Examples of the coating method include spin coating, gravure coating, kiss coating, die coating, lip coating, comma coating, blade coating, roll coating, knife coating, spray coating, bar coating, and dip coating. Among these, spin coating is preferably used as the coating method. That is, the electrolyte membrane 11 may be obtained by spin-coating the chemical solution on the substrate and then drying to form a film.

[0052] The solvent for producing this chemical solution can be appropriately selected depending on the properties of the elastomer and ionic compound.

[0053] Specifically, the solvent may be an organic solvent, such as one or more of alcohol-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents, ether ester-based solvents, glycol ether-based solvents, amide-based solvents, and carbonate-based solvents.

[0054] Examples of alcohol-based solvents include methanol, ethanol, isopropanol, 1-butanol, tertiary butanol, isobutanol, diacetone alcohol, and 3-methoxy-3-methyl-1-butanol. Examples of ketone-based solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and diisobutyl ketone. Examples of ester-based solvents include ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Examples of ether-based solvents include dibutyl ether, tetrahydrofuran, and dioxane. Examples of ether ester-based solvents include 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, and methyl methoxypropionate. Examples of glycol ether solvents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, butyl cellosolve (ethylene glycol monobutyl ether), etc. Examples of amide solvents include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Examples of carbonate solvents include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, etc.

[0055] Among these, in the method for producing a laminate according to the present embodiment, the solvent is preferably an amide solvent, since the elastomer and the ionic compound tend to be homogenized during the membrane formation process, making it easier to obtain a thin electrolyte membrane.

[0056] In the method for manufacturing the laminate 100 of this embodiment, each layer other than the electrolyte membrane 11 is prepared and then laminated. Each layer other than the electrolyte membrane 11 may be prepared according to a known method. When laminating each layer, an adhesive layer made of an adhesive may be provided between the layers. In addition, when using patterned films as the electrodes 12 and the ion exchange layer 13 as described above, each layer (film) may be processed to have a predetermined pattern by, for example, laser ablation.

[0057] In this manner, the laminate 100 of this embodiment is produced. Since such a laminate 100 includes an extremely thin electrolyte membrane 11, it can be used for a variety of purposes.

[0058] <Second embodiment: adhesive laminate / application method> Next, an adhesive laminate and an application method using this adhesive laminate will be described as a second embodiment. Here, the adhesive laminate shown as the second embodiment comprises a laminate and a release film provided as the outermost layer. Note that the laminate constituting a part of the adhesive laminate is typically the laminate shown in the first embodiment. Such an adhesive laminate and specific uses will be described with reference to the drawings.

[0059] Fig. 4 is a cross-sectional view of an example of an adhesive laminate according to the second embodiment. The adhesive laminate 300 shown in Fig. 3 is formed by laminating an electrode 32, an electrolyte membrane 31, and an ion exchange layer 33, with a first insulating layer 34 and a second insulating layer 35 provided as outer layers thereof. Note that these structures are similar to the electrode 12, electrolyte membrane 11, ion exchange layer 13, first insulating layer 14, and second insulating layer 15 shown in the first embodiment.

[0060] 4, a release film 36 is provided on the outermost layer to facilitate application of the laminate 300. Note that this release film 36 is usually removed after application of the laminate.

[0061] The thickness of the release film 36 may be appropriately set depending on the ease of application, etc. As an example, the average thickness of the release film 36 may be in the range of 1 to 50 μm, may be in the range of 3 to 40 μm, or may be in the range of 5 to 30 μm.

[0062] The release film 36 may be removed by various methods. In one embodiment, the release film 36 is mechanically peeled off after the application operation. Alternatively, the release film 36 may be dissolved and removed with a solvent (including water and organic solvents) after the application operation. The embodiment in which the release film 36 is removed with a solvent will be described in detail below.

[0063] That is, assuming a system in which the release film 36 is removed by water, the release film 36 may include a water-soluble polymer. Such a water-soluble polymer may be appropriately selected from a variety of materials. Examples of water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, etc. Among these, from the viewpoint of achieving high performance as a release film, it is preferable that the water-soluble polymer includes polyvinyl alcohol (hereinafter sometimes abbreviated as PVA). Note that PVA here is generally obtained by saponifying polyvinyl acetate. Note that the degree of saponification can be appropriately set depending on the application, etc.

[0064] Next, a description will be given below of an application method using such an adhesive laminate 300. That is, the application method of this embodiment is a method for applying a laminate to the skin, and includes the steps of preparing an adhesive laminate, applying the surface of the adhesive laminate opposite to the side on which the release film is present to the skin, and removing the release film containing a water-soluble polymer using water.

[0065] This application method will be described with reference to Fig. 5. Fig. 5 is a conceptual diagram showing an example of the application method according to the second embodiment. That is, first, an adhesive laminate 300 as shown in Fig. 4 is prepared, and then the surface of the adhesive laminate 300 opposite to the side on which the release film 36 is present is applied to the skin SK (see Fig. 5(a)). Next, water-soaked fibers or the like (referred to as "water W" for convenience) are brought into contact with the release film 36 exposed on the surface (see Fig. 5(b)). As described above, if the release film 36 contains a water-soluble polymer, the release film 36 is dissolved and removed by the water W, resulting in the laminate being applied to the skin SK (see Fig. 5(c)).

[0066] In this manner, the laminate obtained in the first embodiment can be attached to the skin.

[0067] Third Embodiment: Electrolyte Membrane / Electronic Device The third embodiment encompasses an electrolyte membrane and an electronic device using the same. The electrolyte membrane of the third embodiment includes an elastomer and an ionic compound and has an average thickness of 15 μm or less. That is, this electrolyte membrane is similar to the electrolyte membrane shown as electrolyte membrane 11 in the first embodiment. However, the electrolyte membrane of this embodiment does not necessarily have to be applied to the laminate 100. In other words, the electrolyte membrane of the third embodiment may be one provided in an electronic device, but does not necessarily have to be one interposed between the electrode 12 and the ion exchange layer 13. That is, the electrolyte membrane of the third embodiment may be configured to exchange ions in an in-plane direction.

[0068] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0069] Furthermore, it may be provided in the following aspects.

[0070] (1) A laminate comprising an electrode, an electrolyte membrane, and an ion exchange layer that exchanges ions with the electrode, stacked in this order, the electrolyte membrane containing an elastomer and an ionic compound, and the electrolyte membrane having an average thickness of 15 μm or less.

[0071] (2) The laminate according to (1) above, wherein the elastomer contains a heteroatom in its chemical structure.

[0072] (3) In the laminate described in (1) or (2) above, the electrode and / or the ion-exchange layer contains one or more polymers selected from the group consisting of polythiophene, polypyrrole, polyaniline, and polybenzodifurandione.

[0073] (4) In the laminate described in (3) above, the electrode and / or the ion-exchange layer contains a polythiophene having a structural unit represented by the following chemical formula (1): In chemical formula (1), each R is independently an organic group, a hydroxyl group, a mercapto group, an amino group, or a halogen atom, and the structure of R may have an anionic structure as a part thereof, and n is an integer of 0 to 4.

[0074] (5) In the laminate according to (3) or (4), the electrode and / or the ion-exchange layer contains a polybenzodifurandione having a structural unit represented by the following chemical formula (3): In chemical formula (3), R ３１ ~R ３４ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a phenyl group which may have a substituent, and a naphthyl group which may have a substituent.

[0075] (6) The laminate according to any one of (1) to (5) above, wherein at least one of the electrode and the ion-exchange layer is a patterned film.

[0076] (7) The laminate according to any one of (1) to (6) above, which constitutes a part of a display or a transistor.

[0077] (8) The laminate according to any one of (1) to (7) above, further comprising a first insulating layer and a second insulating layer as outer layers of the electrode and the ion exchange layer, respectively.

[0078] (9) A laminate for application, comprising the laminate according to any one of (1) to (8) above and a release film provided as the outermost layer.

[0079] (10) The adhesive laminate according to (9) above, wherein the release film contains a water-soluble polymer.

[0080] (11) A method for applying a laminate to skin, comprising the steps of: preparing the adhesive laminate described in (10) above; applying the surface of the adhesive laminate opposite to the side on which the release film is present to the skin; and removing the release film containing the water-soluble polymer using water.

[0081] (12) A method for producing the laminate described in any one of (1) to (8) above, comprising a step of laminating the electrode, the electrolyte membrane, and the ion exchange layer, wherein the electrolyte membrane is obtained by applying a chemical solution containing the elastomer, the ionic compound, and a solvent to a substrate, and then drying the chemical solution to form a film.

[0082] (13) The method according to (12) above, wherein the solvent is an amide solvent.

[0083] (14) The method according to (12) or (13) above, wherein the electrolyte membrane is obtained by spin-coating the chemical solution onto the substrate and then drying the chemical solution to form a membrane.

[0084] (15) An electrolyte membrane comprising an elastomer and an ionic compound, and having an average membrane thickness of 15 μm or less.

[0085] (16) An electronic device comprising the electrolyte membrane according to (14). Of course, the present invention is not limited to this.

[0086] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0087] [Materials Used] In this example, the following materials were used as the elastomer and ionic compound: Elastomer: Thermoplastic polyurethane elastomer (Miractran P22MBRNAT, manufactured by Nihon Miractoran Co., Ltd.) Ionic compound: 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[0088] In performing the film formation described below, the elastomer is dissolved in N,N-dimethylacetamide (DMAc) in advance to obtain an elastomer solution, and then a predetermined operation is performed. Here, the ionic compound is added to the obtained elastomer solution in a proportion of 20 mass % of the elastomer amount.

[0089] [Film Formation] Solutions having the elastomer concentrations shown in Table 1 were applied to glass substrates by spin coating to form thin films. As shown in Table 1, it was confirmed that the film thickness could be controlled by changing the spin coating conditions (rotation speed, time). The film thickness was measured using a Dektak XT from Bruker.

[0090]

[0091] Although not shown in Table 1, when THF was used as the solvent, a radial pattern appeared during spin coating, and a uniform film could not be obtained.

[0092] [Evaluation of devices using the formed electrolyte membrane] A display was fabricated using the electrolyte membrane obtained under the above conditions A, C, and E, and the color change was confirmed. Specifically, a polythiophene-based conductive polymer "PEDOT:PSS" was formed on both sides of the obtained electrolyte membrane, and the color change was confirmed by setting the on-voltage to 2 V. In this evaluation, the absorbance was measured using a UV-visible spectrophotometer (Shimadzu Corporation, UV-2600i).

[0093] Figure 6 is a graph summarizing the results of evaluation of the devices obtained in the examples. From Figure 6, it was confirmed that even when the electrolyte membrane was thinned to around 1 μm, a spectral shift occurred similar to that obtained under condition A.

[0094] [Verification of Resolution] Separately, a 1.49 μm-thick electrolyte membrane was obtained using the same elastomer and ionic compound as those described above. A device with the structure shown in FIG. 3 was fabricated using this electrolyte membrane. Here, electrodes 12A and 12B were patterned as lines with a width of 30 μm, with a gap of 65 μm between these patterns. A voltage of 2 V was then applied to electrode 12A. FIG. 7 is a photograph showing the results of an evaluation of the device obtained in this example. As shown in FIG. 7, in this example, only electrode 12A changed color, confirming that the color change of electrode 12B was controlled. From this, it can be said that a high-resolution device can be realized by applying a thin electrolyte membrane such as that shown in this example.

[0095] 11, 21, 31: electrolyte membrane, 12, 12A, 12B, 22, 32: electrodes, 13, 23, 33: ion exchange layer, 14, 24, 34: first insulating layer, 15, 25, 35: second insulating layer, 36: release film, 100, 200: laminate, 300: adhesive laminate, SK: skin, W: water

Claims

1. A laminate comprising an electrode, an electrolyte membrane, and an ion exchange layer that exchanges ions with the electrode, stacked in this order, the electrolyte membrane containing an elastomer and an ionic compound, and the average thickness of the electrolyte membrane being 15 μm or less.

2. The laminate according to claim 1, wherein the elastomer contains heteroatoms in its chemical structure.

3. A laminate according to claim 1, wherein the electrode and / or the ion-accepting layer comprises one or more polymers selected from the group consisting of polythiophene, polypyrrole, polyaniline and polybenzodifurandione.

4. In the laminate according to claim 3, the electrode and / or the ion-accepting layer contains a polythiophene having a structural unit represented by the following chemical formula (1): A laminate, wherein in chemical formula (1), R is each independently an organic group, a hydroxyl group, a mercapto group, an amino group or a halogen atom, and the structure of R may have an anionic structure as a part thereof, and n is an integer of 0 to 4.

5. In the laminate according to claim 3, the electrode and / or the ion-accepting layer contains a polybenzodifurandione having a structural unit represented by the following chemical formula (3): In the chemical formula (3), R ３１ ~R ３４ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a phenyl group which may have a substituent, and a naphthyl group which may have a substituent.

6. The laminate according to claim 1, wherein at least one of the electrode and the ion exchange layer is a patterned film.

7. The laminate according to claim 1, which constitutes a part of a display or a transistor.

8. The laminate according to claim 1, further comprising a first insulating layer and a second insulating layer as the outer layer of the electrode and the outer layer of the ion exchange layer, respectively.

9. A laminate for application, comprising: a laminate according to any one of claims 1 to 8; and a release film provided as an outermost layer.

10. The adhesive laminate according to claim 9, wherein the release film contains a water-soluble polymer.

11. A method for applying a laminate to skin, comprising the steps of: preparing the laminate for application as described in claim 10; applying the surface of the laminate for application opposite to the surface on which the release film is present to the skin; and removing the release film containing the water-soluble polymer using water.

12. A method for producing a laminate according to any one of claims 1 to 8, comprising a step of laminating the electrode, the electrolyte membrane, and the ion exchange layer, wherein the electrolyte membrane is obtained by applying a chemical solution containing the elastomer, the ionic compound, and a solvent to a substrate, and then drying the applied solution to form a film.

13. The method of claim 12, wherein the solvent is an amide solvent.

14. The method according to claim 12, wherein the electrolyte membrane is obtained by spin-coating the chemical solution onto the substrate and then drying to form a film.

15. An electrolyte membrane comprising an elastomer and an ionic compound, and having an average membrane thickness of 15 μm or less.

16. An electronic device comprising the electrolyte membrane according to claim 15.

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